WO2007018783A2 - Polymerisation de fluoropolymeres au moyen de tensioactifs non fluores - Google Patents
Polymerisation de fluoropolymeres au moyen de tensioactifs non fluores Download PDFInfo
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- WO2007018783A2 WO2007018783A2 PCT/US2006/024704 US2006024704W WO2007018783A2 WO 2007018783 A2 WO2007018783 A2 WO 2007018783A2 US 2006024704 W US2006024704 W US 2006024704W WO 2007018783 A2 WO2007018783 A2 WO 2007018783A2
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- WO
- WIPO (PCT)
- Prior art keywords
- acid
- polymerization
- reactor
- monomer
- surfactant
- Prior art date
Links
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 75
- 238000006116 polymerization reaction Methods 0.000 title claims abstract description 45
- 229920002313 fluoropolymer Polymers 0.000 title claims abstract description 25
- 239000004811 fluoropolymer Substances 0.000 title claims abstract description 23
- 239000000178 monomer Substances 0.000 claims abstract description 42
- 229920002125 Sokalan® Polymers 0.000 claims abstract description 39
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 30
- 150000003839 salts Chemical class 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 19
- 239000002253 acid Substances 0.000 claims abstract description 16
- 239000003999 initiator Substances 0.000 claims description 49
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical group FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 43
- 239000004584 polyacrylic acid Substances 0.000 claims description 32
- 229920000642 polymer Polymers 0.000 claims description 24
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims description 10
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 229920001577 copolymer Polymers 0.000 claims description 6
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical compound FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 6
- MIZLGWKEZAPEFJ-UHFFFAOYSA-N 1,1,2-trifluoroethene Chemical group FC=C(F)F MIZLGWKEZAPEFJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012431 aqueous reaction media Substances 0.000 claims description 4
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 claims description 4
- 239000000839 emulsion Substances 0.000 claims description 4
- XUCNUKMRBVNAPB-UHFFFAOYSA-N fluoroethene Chemical compound FC=C XUCNUKMRBVNAPB-UHFFFAOYSA-N 0.000 claims description 3
- 230000000977 initiatory effect Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 claims description 2
- 159000000000 sodium salts Chemical group 0.000 claims description 2
- 239000011342 resin composition Substances 0.000 claims 1
- 239000012736 aqueous medium Substances 0.000 abstract description 3
- 238000010526 radical polymerization reaction Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 description 39
- 239000000243 solution Substances 0.000 description 23
- 238000013019 agitation Methods 0.000 description 20
- 239000004816 latex Substances 0.000 description 20
- 229920000126 latex Polymers 0.000 description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 16
- 150000003254 radicals Chemical class 0.000 description 14
- 239000007787 solid Substances 0.000 description 13
- -1 aliphatic azo compound Chemical class 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000003153 chemical reaction reagent Substances 0.000 description 8
- 229910001220 stainless steel Inorganic materials 0.000 description 8
- 239000010935 stainless steel Substances 0.000 description 8
- 239000006172 buffering agent Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000002033 PVDF binder Substances 0.000 description 6
- 239000012986 chain transfer agent Substances 0.000 description 6
- 239000012188 paraffin wax Substances 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 229920001897 terpolymer Polymers 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 5
- 150000007513 acids Chemical class 0.000 description 5
- 238000001816 cooling Methods 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000001632 sodium acetate Substances 0.000 description 5
- 235000017281 sodium acetate Nutrition 0.000 description 5
- 238000012546 transfer Methods 0.000 description 5
- 239000002519 antifouling agent Substances 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 230000014509 gene expression Effects 0.000 description 4
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 238000012674 dispersion polymerization Methods 0.000 description 3
- 238000007720 emulsion polymerization reaction Methods 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- GVEUEBXMTMZVSD-UHFFFAOYSA-N 3,3,4,4,5,5,6,6,6-nonafluorohex-1-ene Chemical group FC(F)(F)C(F)(F)C(F)(F)C(F)(F)C=C GVEUEBXMTMZVSD-UHFFFAOYSA-N 0.000 description 2
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical class C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 239000008351 acetate buffer Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000001246 colloidal dispersion Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 125000003709 fluoroalkyl group Chemical group 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 125000005634 peroxydicarbonate group Chemical group 0.000 description 2
- 239000008363 phosphate buffer Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 229920001169 thermoplastic Polymers 0.000 description 2
- 229920001567 vinyl ester resin Polymers 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
- NDMMKOCNFSTXRU-UHFFFAOYSA-N 1,1,2,3,3-pentafluoroprop-1-ene Chemical compound FC(F)C(F)=C(F)F NDMMKOCNFSTXRU-UHFFFAOYSA-N 0.000 description 1
- ABADUMLIAZCWJD-UHFFFAOYSA-N 1,3-dioxole Chemical class C1OC=CO1 ABADUMLIAZCWJD-UHFFFAOYSA-N 0.000 description 1
- OVSKIKFHRZPJSS-UHFFFAOYSA-N 2,4-D Chemical compound OC(=O)COC1=CC=C(Cl)C=C1Cl OVSKIKFHRZPJSS-UHFFFAOYSA-N 0.000 description 1
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- QMIWYOZFFSLIAK-UHFFFAOYSA-N 3,3,3-trifluoro-2-(trifluoromethyl)prop-1-ene Chemical group FC(F)(F)C(=C)C(F)(F)F QMIWYOZFFSLIAK-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-UHFFFAOYSA-N Di-Et ester-Fumaric acid Natural products CCOC(=O)C=CC(=O)OCC IEPRKVQEAMIZSS-UHFFFAOYSA-N 0.000 description 1
- IEPRKVQEAMIZSS-WAYWQWQTSA-N Diethyl maleate Chemical compound CCOC(=O)\C=C/C(=O)OCC IEPRKVQEAMIZSS-WAYWQWQTSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910004727 OSO3H Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- UEKQGZQLUMSLNW-UHFFFAOYSA-N Propyl isome Chemical compound C1=C2C(C(=O)OCCC)C(C(=O)OCCC)C(C)CC2=CC2=C1OCO2 UEKQGZQLUMSLNW-UHFFFAOYSA-N 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical class C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 230000003466 anti-cipated effect Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- YOALFLHFSFEMLP-UHFFFAOYSA-N azane;2,2,3,3,4,4,5,5,6,6,7,7,8,8,8-pentadecafluorooctanoic acid Chemical compound [NH4+].[O-]C(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F YOALFLHFSFEMLP-UHFFFAOYSA-N 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 230000006583 body weight regulation Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000002144 chemical decomposition reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000013626 chemical specie Substances 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000012933 diacyl peroxide Substances 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- IEPRKVQEAMIZSS-AATRIKPKSA-N diethyl fumarate Chemical compound CCOC(=O)\C=C\C(=O)OCC IEPRKVQEAMIZSS-AATRIKPKSA-N 0.000 description 1
- LDCRTTXIJACKKU-ONEGZZNKSA-N dimethyl fumarate Chemical compound COC(=O)\C=C\C(=O)OC LDCRTTXIJACKKU-ONEGZZNKSA-N 0.000 description 1
- 229960004419 dimethyl fumarate Drugs 0.000 description 1
- LDCRTTXIJACKKU-ARJAWSKDSA-N dimethyl maleate Chemical compound COC(=O)\C=C/C(=O)OC LDCRTTXIJACKKU-ARJAWSKDSA-N 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- FNMTVMWFISHPEV-AATRIKPKSA-N dipropan-2-yl (e)-but-2-enedioate Chemical compound CC(C)OC(=O)\C=C\C(=O)OC(C)C FNMTVMWFISHPEV-AATRIKPKSA-N 0.000 description 1
- FNMTVMWFISHPEV-WAYWQWQTSA-N dipropan-2-yl (z)-but-2-enedioate Chemical compound CC(C)OC(=O)\C=C/C(=O)OC(C)C FNMTVMWFISHPEV-WAYWQWQTSA-N 0.000 description 1
- DSTWFRCNXMNXTR-AATRIKPKSA-N dipropyl (e)-but-2-enedioate Chemical compound CCCOC(=O)\C=C\C(=O)OCCC DSTWFRCNXMNXTR-AATRIKPKSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- MEGHWIAOTJPCHQ-UHFFFAOYSA-N ethenyl butanoate Chemical compound CCCC(=O)OC=C MEGHWIAOTJPCHQ-UHFFFAOYSA-N 0.000 description 1
- UIWXSTHGICQLQT-UHFFFAOYSA-N ethenyl propanoate Chemical compound CCC(=O)OC=C UIWXSTHGICQLQT-UHFFFAOYSA-N 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 125000004428 fluoroalkoxy group Chemical group 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000002563 ionic surfactant Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000004530 micro-emulsion Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000013386 optimize process Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 239000011734 sodium Chemical class 0.000 description 1
- 239000007974 sodium acetate buffer Substances 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
- C08F214/22—Vinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/18—Monomers containing fluorine
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/04—Polymerisation in solution
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F214/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F214/18—Monomers containing fluorine
Definitions
- the present invention relates to a method for the polymerization in an aqueous medium of monomers, and especially of fluoromonomers, using non-fluorinated surfactants; and the fluoropolymers formed therefrom.
- the method of the polymerization uses one or more non-fluorinated surfactants selected from the group consisting of polyvinylphosphonic acid, polyacrylic acids, polyvinyl sulfonic acid, and salts thereof.
- non-fluorinated surfactants selected from the group consisting of polyvinylphosphonic acid, polyacrylic acids, polyvinyl sulfonic acid, and salts thereof.
- the use of polyvinylphosphonic acid, polyacrylic acids, polyvinyl sulfonic acid as surfactants in aqueous free radical polymerization is also novel.
- Fluoropolymers are primarily produced via heterogeneous polymerization reactions, including suspension, emulsion and microemulsion systems. Generally, each of these reactions requires at least one monomer and a radical initiator in a suitable reaction medium.
- emulsion polymerizations of halogen- containing monomers generally require a surfactant capable of emulsifying both the reactants and the reaction products for the duration of the polymerization reaction.
- the surfactant of choice in the synthesis of fluoropolymers is generally a perfluoroalkyl surfactant.
- the most common perfluoroalkyl surfactant in the production of halogenated polymers is ammonium perfluorooctanoate (AFPO).
- Fluorosurfactants are expensive, specialized materials, however. In addition, because of their high stability, they tend to persist in the environment. Because of their resistance to chemical degradation, fluoroalkyl surfactants have the potential to accumulate in the environment and in organisms. Also, the high degree of fluorination of the surfactant avoids atom transfer between a growing polymer chain and the surfactant during polymerization, which will result in lowered molecular weights in the product and likely inhibition of the reaction. New polymerization processes are needed that utilize non-perfluoroalkyl surfactants or reduced amounts of perfluoroalkyl surfactants.
- Patent US 2 559 752 assigned to E. I. du Pont de Nemours relates to an "Aqueous colloidal dispersions of polymers".
- Stable aqueous colloidal dispersions of polymerized ethylenically unsaturated, organic compounds are obtained by carrying out the polymerization in the presence of a H 2 O-soluble polymerization initiator, such as an alkali persulfate or an aliphatic azo compound (cf. U.S. patent 2,471,959, CA. 43, 6002g), and a polyfluorinated ionizable dispersing agent (I).
- the I is taken from various groups of compounds including:
- polyvinyl phosphonic acid, polyacrylic acids, polyvinyl sulfonic acid or their salts could be used as surfactants in the aqueous-based synthesis of polymers, and especially of fluorinated polymers, and thereby eliminate or significantly reduce the use of fluorinated surfactants.
- the invention relates to a process for preparing a fluoropolymer in an aqueous reaction medium comprising: a) forming an aqueous emulsion comprising at least one radical initiator, at least one non-flourinated surfactants, and at least one fluoromonomer, and b) initiating polymerization of said fluoromonomer, wherein said non-fluorinated surfactant is selected from the group consisting of polyvinylphosphonic acid, polyacrylic acid, polyvinyl sulfonic acid, and the salts thereof.
- the invention further relates to a fluoropolymer resin formed in an aqueous medium using non-fluorinated surfactant selected from the group consisting of polyvinylphosphonic acid, polyacrylic acid, polyvinyl sulfonic acid, and the salts thereof.
- the invention relates to the polymerization of fluoropolymers using as the surfactant polyvinylphosphonic acid, polyacrylic acids, and/or polyvinyl sulfonic acid, and the salts thereof.
- a polymerization reaction is carried out by charging a reactor with water (preferably deionized water), at least one non- fluorinated surfactant, at least one monomer, preferably at least one fluoromonomer, and optionally, a chain-transfer agent and an antifoulant. Air may be purged from the reactor prior to the introduction of the fluoromonomer. Water is added to the reactor before bringing the reactor to the desired starting temperature, but the other materials may be added before or after bringing the reactor to temperature. At least one radical initiator is added to start and maintain the polymerization reaction. Additional monomer may be optionally added to replenish monomer that is consumed, and the other materials may be optionally added during the course of the polymerization to maintain the reaction and control the final product properties.
- surfactant means a type of molecule which has both hydrophobic and hydrophilic portions, which allows it to stabilize and disperse hydrophobic molecules and aggregates of hydrophobic molecules in aqueous systems.
- the poly acids of the invention include the acid, as well as the fully or partially neutralized acids, preferably as the ammonium or sodium salts.
- Polyacrylic acid includes both polyacrylic acid and polymethacrylic acid.
- the polyacrylic acid, polyvinyl sulfonic acid and polyvinyl phosphonic acid surfactants are used at from 0.001-2 wt%, preferably 0.001-0.5 wt %, base on total monomer.
- alkyl phosphonic acid, polyphosphonic acid, polyacrylic acid, and polyvinyl sulfonic acid surfactants and their salts of the invention are all water-soluble or water-dispersible, low molecular weight molecules.
- the polyvinyl phosphonic acid, polyacrylic acid, and polyvinyl sulfonic acid surfactants of the invention includes copolymers of the acids with one or more other ethylenically unsaturated monomers, and the copolymer itself must be water soluble or water dispersible.
- Other co-surfactants can also be used with polyvinyl phosphonic acid, polyacrylic acid, and polyvinyl sulfonic acid surfactants of the invention.
- Preferred co-surfactants are non-fluorinated hydrocarbon surfactants, a siloxane surfactant or a combination thereof.
- the monomers useful in the aqueous-based polymerization of the invention using polyvinyl phosphonic acid, polyacrylic acid, and polyvinyl sulfonic acid surfactants are any ethylenically unsaturated monomers.
- Useful monomers include, but are not limited to acrylic acid and acrylic esters such as alkyl(meth) acrylates, vinyl esters such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl benzoate, maleic esters such as dimethyl maleate, diethyl maleate, di-n-propyl maleate, diisopropyl maleate, di-2-methoxyethyl maleate, fumaric esters such as dimethyl fumarate, diethyl fumarate, di-n-propyl fumarate, diisopropyl fumarate, styrene, vinyltoluene, alpha-methylstyrene and acrylonitrile. anhydrides, vinyl esters, alpha- o
- fluoromonomer or the expression “fluorinated monomer” means a polymerizable alkene which contains at least one fluorine atom, fluoroalkyl group, or fluoroalkoxy group attached to the double bond of the alkene that undergoes polymerization.
- fluoropolymer means a polymer formed by the polymerization of at least one fluoromonomer, and it is inclusive of homopolymers, copolymers, terpolymers and higher polymers which are thermoplastic in their nature, meaning they are capable of being formed into useful pieces by flowing upon the application of heat, such as is done in molding and extrusion processes.
- the fluoropolymer preferably contains at least 50 mole percent of one or more flouromonomers.
- the thermoplastic polymers typically exhibit a crystalline melting point.
- Fluoromonomers useful in the practice of the invention include, for example, vinylidene fluoride (VF 2 ), tetrafluoroethylene (TFE), trifiuoroethylene, chlorotrifluoroethylene (CTFE), hexafluoropropene (HFP), vinyl fluoride, hexafluoroisobutylene, perfluorobutylethylene (PFBE), pentafluoropropene, 3,3,3- trifluoiO-l-propene, 2-trifluoiOmethyl-3,3,3-trifluoropropene a fluorinated vinyl ether, a fluorinated allyl ether, a non-fluorinated allyl ether, a fluorinated dioxole, and combinations thereof.
- VF 2 vinylidene fluoride
- TFE tetrafluoroethylene
- CTFE chlorotrifluoroethylene
- HFP hexafluoropropene
- Especially preferred copolymers made by the process of the invention are copolymers comprising from about 71 to about 99 weight percent VDF 5 and correspondingly from about 1 to about 29 percent TFE; from about 71 to 99 weight percent VDF, and correspondingly from about 1 to 29 percent HFP (such as disclosed in U.S. Pat. No. 3,178,399); and from about 71 to 99 weight percent VDF, and correspondingly from about 1 to 29 weight percent trifluoroethylene.
- Especially preferred terpolymers are the terpolymer of VDF, HFP and TFE, and the terpolymer of VDF, trifluoroethene, and TFE.
- the especially preferred terpolymers have at least 10 weight percent VDF, and the other comonomers may be present in varying portions, but together they comprise up to 90 weight percent of the terpolymer.
- initiator and the expressions "radical initiator” and “free radical initiator” refer to a chemical that is capable of providing a source of free radicals, either induced spontaneously, or by exposure to heat or light. Examples of initiators include peroxides, peroxydicarbonates and azo compounds. The term expression also includes redox systems useful in providing a source of free radicals.
- radical and the expression “free radical” refer to a chemical species that contains at least one unpaired electron.
- the radical initiator is added to the reaction mixture in an amount sufficient to initiate and maintain the polymerization reaction at a desired reaction rate.
- the order of addition may vary according to the desired process and latex emulsion characteristics.
- the radical initiator may comprise a persulfate salt, such as sodium persulfate, potassium persulfate, or ammonium persulfate.
- a persulfate salt such as sodium persulfate, potassium persulfate, or ammonium persulfate.
- the amount of persulfate salt added to the reaction mixture is from about 0.005 to about 1.0 weight percent.
- the radical initiator may comprise an organic peroxide such as an alkyl, dialkyl, or diacyl peroxide, peroxydicarbonates, and peroxy esters in an amount from about 0.5 to about 2.5 weight percent on total monomer.
- organic peroxide such as an alkyl, dialkyl, or diacyl peroxide, peroxydicarbonates, and peroxy esters in an amount from about 0.5 to about 2.5 weight percent on total monomer.
- Chain-transfer agents are added to the polymerization to regulate the molecular weight of the product. They may added to a polymerization in a single portion at the beginning of the reaction, or incrementally or continuously throughout the reaction.
- the amount and mode of addition of chain-transfer agent depend on the activity of the particular chain-transfer agent employed, and on the desired molecular weight of the polymer product.
- the amount of chain-transfer agent added to the polymerization reaction is preferably from about 0.05 to about 5 weight percent, more preferably from about 0.1 to about 2 weight percent based on the total weight of monomer added to the reaction mixture.
- chain transfer agents useful in the present invention include, but are not limited to oxygenated compounds such as alcohols, carbonates, ketones, esters, and ethers may serve as chain-transfer agents; halocarbons and hydrohalocarbons, such as chlorocarbons, hydrochlorocarbons, chlorofluorocarbons and hydrochlorofluorocarbons; ethane and propane.
- the polymerization reaction mixture may optionally contain a buffering agent to maintain a controlled pH throughout the polymerization reaction.
- the pH is preferably controlled within the range of from about 4 to about 8, to minimize undesirable color development in the product.
- Buffering agents may comprise an organic or inorganic acid or alkali metal salt thereof, or base or salt of such organic or inorganic acid, that has at least one pK a value and/or pK b value in the range of from about 4 to about 10, preferably from about 4.5 to about 9.5.
- Preferred buffering agents in the practice of the invention include, for example, phosphate buffers and acetate buffers.
- a "phosphate buffer” is a salt or salts of phosphoric acid.
- An “acetate buffer” is a salt of acetic acid.
- Buffering agents are preferably employed where potassium persulfate is employed as the radical initiator.
- a preferred buffering agent for use with persulfate radical initiators is sodium acetate.
- a preferred amount of sodium acetate buffer is from about 50 wt.% to about 150 wt.%, based on the weight of persulfate initiator added to the reaction.
- the addition of a paraffin wax or hydrocarbon oil to the reaction serves as an antifouling to minimize or prevent polymer adhesions to the reactor components. Any long chain saturated hydrocarbon wax or oil can perform this function.
- the amount of oil or wax added to the reactor is an amount which serves to minimize the formation of polymer adhesions to the reactor components. The amount is generally proportional to the interior surface area of the reactor and may vary from about 1 to about 40 mg per square centimeter of reactor interior surface area.
- the amount of paraffin wax or hydrocarbon oil is preferably about 5 mg/cm 2 of the reactor interior surface area.
- the temperature used for polymerization may vary from 20-160 degrees Celsius, depending on the initiator system chosen.
- the polymerization temperature is preferably from 35-130 degrees Celsius, and most preferably from 65-130 degrees Celsius. In one embodiment, the temperature is varied during the reaction.
- the pressure used for polymerization may vary from 280-20,000 kPa, depending on the capabilities of the reaction equipment, the initiator system chosen, and the monomer selection.
- the polymerization pressure is preferably from 2,000- 11,000 kPa, and most preferably from 2,750-6,900 IdPa.
- the polymerization occurs under stirring.
- the stirring may be constant, or may be varied to optimize process conditions during the course of the polymerization. In one embodiment, both multiple stirring speeds and multiple temperatures are used for controlling the reaction.
- a pressurized polymerization reactor equipped with a stirrer and heat control means is charged with water, preferably deionized water, one or more of the surfactants of the invention and at least one fluoromonomer.
- the mixture may optionally contain one or more of an additional non-fluorinated surfactant, a buffering agent, an antifoulant and a chain- transfer agent for molecular weight regulation of the polymer product.
- air Prior to introduction of the monomer or monomers, air is preferably removed from the reactor in order to obtain an oxygen-free environment for the polymerization reaction.
- the order in which the polymerization components are assembled may be varied, provided that the surfactant of the invention is present in the aqueous reaction medium prior to the initiation of the polymerization of the fluoromonomer.
- water, initiator, surfactant and optionally antifoulant, chain transfer agent and buffer are charged to the reactor, and the reactor heated to the desired reaction temperature.
- the monomer(s) is then fed into the reactor, preferably at a rate which provides an essentially constant pressure.
- the monomer and initiator can be fed to the reactor, along with one or more of the optional ingredients.
- Other variations for fluoropolymer polymerization processes are anticipated, as known in the art.
- the reactor pressure is primarily regulated by controlling the feed of gaseous monomer to the reaction.
- the reaction pressure is typically from about 280 to about 20,000 IdPa, preferably from about 2,000 to about 11,000 IcPa, more preferably from about 2,750 to about 6,900 kPa.
- the monomer feed is terminated when the desired weight of monomer has been fed to the reactor. Additional radical initiator is optionally added, and the reaction is allowed to react out for a suitable amount of time.
- the reactor pressure drops as the monomer within the reactor is consumed.
- the reactor Upon completion of the polymerization reaction, the reactor is brought to ambient temperature and the residual unreacted monomer is vented to atmospheric pressure.
- the aqueous reaction medium containing the polymer (fluoropolymer) is then recovered from the reactor as a latex.
- the latex consists of a stable mixture of the reaction components, i.e., water, surfactant, initiator (and/or decomposition products of the initiator) and fluoropolymer solids. Generally, the latex contains from about 10 to about 50 weight percent polymer solids.
- the polymer in the latex is in the form of small particles having a size range of from about 30 nm to about 500 nm.
- the product of the polymerization is a latex which can be used in that form, usually after filtration of solid byproducts from the polymerization process, or which can be coagulated to isolate the solids, which may then be washed and dried.
- the latex can be stabilized by the addition of further surfactant, which may be the same or a different ionic surfactant, or may be of a different type, such as an non-ionic surfactant.
- the latex may be coagulated mechanically or by the addition of salts or acids, and then isolated by well-known means such as by filtration. Once isolated, solid product can be purified by washing or other techniques, and it may be dried for use as a powder, which can be further process into granules.
- Vinylidene fluoride homopolymer was made using polyacrylic acid surfactant with potassium persulfate initiator.
- the experiments were carried out in a 25 ml reactor (Endeavor reactor from Argonaut) in which were added 480 micro liter of a 0.25 wt % aqueous surfactant solution (i.e 300 ppm) and 250 micro liter of a 1 wt % aqueous solution of potassium persulfate (i.e 625 ppm). Then deionized water was added to bring the total reactor charge to 4 g. The reactor was purged with nitrogen gas. The reactor was sealed, and agitation is started at 500 rpm. Agitation was maintained throughout the experiment.
- the reactor was heated to 83 0 C.
- the reactor was charged with vinylidene fluoride till the pressure reached was 490 psi.
- the reaction temperature was held at 83 0 C, and the reaction pressure was maintained at 490 psi by adding vinylidene fluoride as needed.
- the amount of VF 2 consumed reached the desired level the VF 2 feed was stopped.
- agitation was continued and the temperature was maintained.
- the agitation and heating were discontinued.
- Table 1 The Examples are summarized in Table 1.
- Table 1 Examples of polyacrylic acid used as surfactant in VDF polymerization.
- Coag latex coagulated.
- L7210 is a surfactant from Rhodia and was used as received
- Polyvinylidene Fluoride was made using Poly Acrylic Acid Surfactant and Potassium Persulfate (KPS) Initiator. Deionized water was used. Reagents were of ACS reagent grade quality unless stated otherwise. Polyacrylic acid was received as a 45 wt% solution. To a 7.5 liter, stainless steel reactor was added 4030 g of water, 4 g of paraffin wax, 100.0 g of an aqueous surfactant solution 1.26 wt% in polyacrylic acid, and 100 g of an aqueous initiator solutionl.2 wt.% in potassium persulfate and 0.72 wt.% in sodium acetate.
- KPS Potassium Persulfate
- the mixture was purged with argon and agitated for 0.5 hours.
- the reactor was sealed, agitation was continued, and the reactor was heated to 121 degrees Celsius.
- the reactor was charged with 362 g of vinylidene fluoride to a pressure of 4454 kPa.17 g of initiator solution was first charged at 240 g/hr followed by a steady feed of initiator solution at a rate of about 60.0 g/h.
- the reaction temperature was held at 121 degrees Celsius, and the reaction pressure was maintained at 4480 kPa by adding as needed vinylidene fluoride. After 1.65 hours, the feed of vinylidene fluoride was stopped. An amount of vinylidene fluoride, 2202 g, had been added to the reactor.
- Polyvinylidene Fluoride was made using Poly Acrylic Acid Surfactant and Potassium Persulfate (KPS) Initiator. Deionized water was used. Reagents were of ACS reagent grade quality unless stated otherwise. Polyacrylic acid was received as a 45 wt% solution. To a 7.5 liter, stainless steel reactor was added 4330 g of water, 4 g of paraffin wax, and 100.0 g of an aqueous surfactant solution 1.31 wt% in polyacrylic acid. The mixture was purged with argon and agitated for 0.5 hours. The reactor was sealed, agitation was continued, and the reactor was heated to 121 degrees Celsius.
- KPS Potassium Persulfate
- the reactor was charged with 362 g of vinylidene fluoride to a pressure of 4454 kPa.19 g of an aqueous initiator solutionl.2 wt.% in potassium persulfate and 0.72 wt.% in sodium acetate was first charged at 120 g/hr followed by a steady feed of initiator solution at a rate of about 60.0 g/h. After 75 min into the run, initiator solution feed rate was dropped to 36 g/h and maintained throughout the rest of the reaction. The reaction temperature was held at 121 degrees Celsius, and the reaction pressure was maintained at 4480 kPa by adding as needed vinylidene fluoride. After 1.87 hours, the feed of vinylidene fluoride was stopped.
- Polyvinylidene Fluoride was made using Poly Acrylic Acid Surfactant and Potassium Persulfate (KPS) Initiator. Deionized water was used. Reagents were of ACS reagent grade quality unless stated otherwise. Polyacrylic acid was received as a 45 wt% solution. To a 7.5 liter, stainless steel reactor was added 4330 g of water, 4 g of paraffin wax, and 100.0 g of an aqueous surfactant solution 0.63 wt% in polyacrylic acid. The mixture was purged with argon and agitated for 0.5 hours. The reactor was sealed, agitation was continued, and the reactor was heated to 121 degrees Celsius.
- KPS Potassium Persulfate
- the reactor was charged with 432 g of vinylidene fluoride to a pressure of 4454 IdPa.13 g of an aqueous initiator solution 1.2 wt.% in potassium persulfate and 0.72 wt.% in sodium acetate was first charged at 72g/hr followed by a steady feed of initiator solution at a rate of about 36.0 g/h. After 90 min into the run, initiator solution feed rate was dropped to 24 g/h and maintained throughout the run. The reaction temperature was held at 121 degrees Celsius, and the reaction pressure was maintained at 4480 IcPa by adding as needed vinylidene fluoride. After 1.87 hours, the feed of vinylidene fluoride was stopped.
- Poly vinylidene Fluoride was made using a mixed polyacrylic acid and T-5863 Polysiloxane surfactant and Potassium Persulfate (KPS) as Initiator. Deionized water was used. Reagents were of ACS reagent grade quality unless stated otherwise. Polyacrylic acid was received as a 45 wt% solution and T-5863 was 100% pure.
- KPS Potassium Persulfate
- the reactor was charged with 478 g of vinylidene fluoride to a pressure of 4454 lcPa.64 g of initiator solution was first charged at 36 g/hr followed by a steady feed of initiator solution throughout the reaction.
- the reaction temperature was held at 121 degrees Celsius, and the reaction pressure was maintained at 4480 IdPa by adding as needed vinylidene fluoride. After 2.6 hours, the feed of vinylidene fluoride was stopped. An amount of vinylidene fluoride, 2200 g, had been added to the reactor. For a period of 0.3 hours, agitation was continued, the temperature was maintained, and the feed of aqueous initiator solution was continued.
- Table 2 PVDF polymerization reactions using Polyacrylic acid as the sole surfactant. All concentrations are on VDF.
- Polysiloxane mixed surfactants All concentrations are on VDF.
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Abstract
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EP06773949.0A EP1922340B1 (fr) | 2005-08-08 | 2006-06-26 | Polymerisation de fluoropolymeres au moyen de tensioactifs non fluores |
CN2006800294282A CN101243108B (zh) | 2005-08-08 | 2006-06-26 | 使用非氟化的表面活性剂聚合含氟聚合物 |
JP2008526003A JP5106396B2 (ja) | 2005-08-08 | 2006-06-26 | 非フッ素化界面活性剤を用いたフルオロポリマーの重合 |
ES06773949.0T ES2611988T3 (es) | 2005-08-08 | 2006-06-26 | Polimerización de fluoropolímeros usando tensioactivos no fluorados |
KR1020087003228A KR101298057B1 (ko) | 2005-08-08 | 2006-06-26 | 비불소화 계면활성제를 사용하는 플루오로중합체의 중합 |
US11/995,593 US8697822B2 (en) | 2005-08-08 | 2006-06-26 | Polymerization of fluoropolymers using non-fluorinated surfactants |
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Cited By (25)
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EP1945684A4 (fr) * | 2005-11-10 | 2010-09-22 | Arkema Inc | Fluoropolymeres ramifies |
CN101293940A (zh) * | 2007-04-29 | 2008-10-29 | 上海远东氟材料技术有限公司 | 拒水拒油的含氟丙烯酸阳离子/非离子表面活性剂乳液的制备方法 |
EP2611840A4 (fr) * | 2010-09-01 | 2014-02-12 | Arkema Inc | Procédé de fabrication de polymères fluorés à l'aide de monomères fonctionnalisés par acide |
EP2686354A4 (fr) * | 2011-03-16 | 2014-10-15 | Arkema Inc | Synthèse de fluoropolymères contenant du 2,3,3,3-tétrafluoropropène |
EP3059265A1 (fr) | 2015-02-23 | 2016-08-24 | 3M Innovative Properties Company | Polymères fluorés durcissables au peroxyde pouvant être obtenus par polymérisation avec des émulsifiants non fluorés |
US10875948B2 (en) | 2015-02-23 | 2020-12-29 | 3M Innovative Properties Company | Peroxide curable fluoropolymers obtainable by polymerization with non-fluorinated emulsifiers |
US11643484B2 (en) * | 2015-03-16 | 2023-05-09 | Arkema Inc. | Modified fluoropolymers |
US12018105B2 (en) | 2018-05-09 | 2024-06-25 | 3M Innovative Properties Company | Fluoropolymers with very low amounts of a fluorinated alkanoic acid or its salts |
EP4194474A4 (fr) * | 2020-08-05 | 2024-08-21 | Daikin Industries, Ltd. | Procédé de fabrication de dispersion aqueuse d'élastomère fluoré |
WO2023227846A1 (fr) | 2022-05-24 | 2023-11-30 | Arkema France | Dispositif électrochimique comprenant un séparateur contenant du pvdf et une composition électrolytique à viscosité élevée ou à haute polarité |
FR3136119A1 (fr) | 2022-05-24 | 2023-12-01 | Arkema France | Dispositif électrochimique comprenant un séparateur contenant du PVDF et une composition électrolytique à viscosité élevée ou à haute polarité |
WO2024052625A1 (fr) | 2022-09-09 | 2024-03-14 | Arkema France | Composition à base d'au moins un polymère fluoré et d'au moins un polymère hydrophile pour revêtement de séparateur |
FR3139575A1 (fr) | 2022-09-09 | 2024-03-15 | Arkema France | Composition à base d’au moins un polymère fluoré et d’au moins un polymère hydrophile pour revêtement de séparateur ou liant de cathode |
WO2024052624A1 (fr) | 2022-09-09 | 2024-03-14 | Arkema France | Composition sous forme de poudre à base d'au moins un polymère fluoré et d'au moins un polymère hydrophile pour revêtement de séparateur ou liant de cathode |
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FR3139570A1 (fr) | 2022-09-09 | 2024-03-15 | Arkema France | Composition à base d’au moins un polymère fluoré et d’au moins un polymère hydrophile pour revêtement de séparateur |
FR3139571A1 (fr) | 2022-09-09 | 2024-03-15 | Arkema France | Composition sous forme de poudre à base d’au moins un polymère fluoré et d’au moins un polymère hydrophile pour revêtement de séparateur ou liant de cathode |
WO2024052623A1 (fr) | 2022-09-09 | 2024-03-14 | Arkema France | Composition à base d'au moins un polymère fluoré et d'au moins un polymère hydrophile pour revêtement de séparateur ou liant de cathode |
FR3139574A1 (fr) | 2022-09-09 | 2024-03-15 | Arkema France | Composition sous forme de poudre à base d’au moins un polymère fluoré et d’au moins un polymère hydrophile pour revêtement de séparateur |
FR3139573A1 (fr) | 2022-09-09 | 2024-03-15 | Arkema France | Composition à base d’au moins un polymère fluoré et d’au moins un polymère hydrophile pour revêtement de séparateur |
WO2024052627A1 (fr) | 2022-09-09 | 2024-03-14 | Arkema France | Composition à base d'au moins un polymère fluoré et d'au moins un polymère hydrophile pour revêtement de séparateur |
WO2024052626A1 (fr) | 2022-09-09 | 2024-03-14 | Arkema France | Composition sous forme de poudre à base d'au moins un polymère fluoré et d'au moins un polymère hydrophile pour revêtement de séparateur |
WO2025008597A1 (fr) | 2023-07-06 | 2025-01-09 | Arkema France | Liant sous forme de poudre pour la préparation d'une électrode dans un procédé sans solvant |
FR3150810A1 (fr) | 2023-07-06 | 2025-01-10 | Arkema France | Liant sous forme de poudre pour la préparation d’une électrode dans un procédé sans solvant |
Also Published As
Publication number | Publication date |
---|---|
US20090221776A1 (en) | 2009-09-03 |
WO2007018783A3 (fr) | 2007-04-05 |
JP5106396B2 (ja) | 2012-12-26 |
JP2009504841A (ja) | 2009-02-05 |
ES2611988T3 (es) | 2017-05-11 |
EP1922340A4 (fr) | 2009-06-03 |
KR101298057B1 (ko) | 2013-08-20 |
US8697822B2 (en) | 2014-04-15 |
CN101243108A (zh) | 2008-08-13 |
EP1922340A2 (fr) | 2008-05-21 |
KR20080032170A (ko) | 2008-04-14 |
CN101243108B (zh) | 2012-08-22 |
EP1922340B1 (fr) | 2016-12-28 |
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